TWI667263B - Method for producing cyclic olefin copolymer - Google Patents

Abstract

The invention provides a method for producing a copolymer, which can obtain a cyclic olefin copolymer having a low molecular weight and a high molecular weight, and is suitable for ordinary molding and processing.

The method for producing a copolymer of the present invention includes: at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin derived from C4 to C12 in the presence of a titanocene catalyst. The polymerization step in which the monomer (B) is polymerized to obtain a copolymer is that the amount of the above-mentioned copolymer obtained in the above-mentioned polymerization step is equivalent to 1,000 g or more per 1 g of the above-mentioned titanocene catalyst, and the number average molecular weight of the above-mentioned copolymer It is 20,000 to 200,000.

Description

Method for producing cyclic olefin copolymer

The present invention relates to a method for producing a cyclic olefin copolymer.

Cyclic olefin polymers and cyclic olefin copolymers (also referred to as "COP" and "COC", respectively), have low hygroscopicity and high transparency, and are used in optical disk substrates, optical films, and optical fibers. A wide range of applications, including fields of materials. Typical COCs are copolymers of cyclic olefins and ethylene. Since the glass transition temperature of the copolymer can be changed by the copolymerization composition of cyclic olefins and ethylene, the glass transition temperature (Tg) can be made higher than COP. Copolymers can achieve a Tg of more than 200 ° C, which is difficult to achieve with COP, but have hard and brittle properties, low mechanical strength, and poor handling and processability problems.

In addition, although there are various polymers with high Tg, these have polar groups, and therefore have limited hygroscopicity and dielectric properties. Therefore, a high Tg polymer having no polar group and consisting of an olefin-based skeleton, excellent optical characteristics, dielectric characteristics, and mechanical strength is required.

As a method for improving the mechanical strength of high TgCOC, there is a method of copolymerizing with a cyclic olefin and an α-olefin other than ethylene (hereinafter, referred to as a "specific α-olefin"). Various studies have been made on the copolymerization of cyclic olefins and specific α-olefins.

The copolymerization of a cyclic olefin with a specific α-olefin is greatly different from the copolymerization of a cyclic olefin with ethylene. Available in the copolymerization of cyclic olefins and ethylene The condition for the high molecular weight body is that the copolymerization of a cyclic olefin and a specific α-olefin has a chain transfer reaction due to the specific α-olefin, and it has been difficult to obtain a high molecular weight body. Therefore, a copolymer of a cyclic olefin and a specific α-olefin is not suitable for a molding material (see, for example, Non-Patent Document 1).

Patent Document 1 describes that a high molecular weight body composed of a cyclic olefin and a specific α-olefin is obtained by using a specific Ti-based catalyst. The Tg is 245 to 262 ° C, the moisture absorption is low, and the linear expansion coefficient is less than 80 ppm Film with excellent physical properties. However, with the polymerization method disclosed in Patent Document 1, since a large amount of catalysts and promoters are used, it is difficult to save resources, and it takes a high cost to obtain a copolymer, and catalysts and promoters remain. The problem is that the transparency of the film is impaired. Further, in Patent Document 1, it is described that 92-164 g of a copolymer can be obtained per 1 g of the catalyst equivalent.

Patent Document 2 discloses a thin film having excellent puncture characteristics, but the Tg is less than 170 ° C. In addition, since Patent Document 2 uses a large amount of catalysts and co-catalysts, it is difficult to save resources, and the cost of obtaining a copolymer is high. At the same time, the transparency and thermal stability of the film are impaired. Furthermore, Patent Document 2 describes that 127-275 g of a copolymer can be obtained per 1 g of the catalyst equivalent.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-298999

[Patent Document 2] Japanese Patent No. 5017222

[Non-patent literature]

[Non-Patent Literature 1] Jung, H. Y., Polyhedron, 2005, Vol. 24, p. 1269-1273

The present invention has been made in view of the above circumstances, and is intended to produce a copolymer of a cyclic olefin copolymer having a molecular weight that is excellent in mechanical properties and suitable for general molding and processing, and which can provide a smaller amount of catalyst and more suitable mechanical properties. The method is the goal.

The present inventors have found that the use of a smaller amount of a titanocene catalyst can obtain more cyclic olefin copolymers with excellent mechanical properties and a molecular weight suitable for ordinary molding and processing, thereby completing the present invention. More specifically, the present invention provides the following.

(1) A method for producing a copolymer, comprising: at least cyclic olefin monomer (A) derived from norbornene and α-olefin derived from C4 to C12 in the presence of a titanocene catalyst; The polymerization step of polymerizing an olefin monomer (B) to obtain a copolymer is that the amount of the above-mentioned copolymer obtained in the above-mentioned polymerization step is 1000 g or more per 1 g of the above-mentioned titanocene catalyst, and the number of the above-mentioned copolymers is average The molecular weight is from 20,000 to 200,000.

(2) The manufacturing method according to (1), wherein the polymerization step is performed in the presence of a promoter and a chain transfer agent composed of an alkylalumoxane together with the titanocene catalyst.

(3) The production method according to (2), wherein the chain transfer agent is an aluminum alkyl.

(4) The manufacturing method according to (3), wherein the alkyl aluminum system is methyl aluminum.

(5) The manufacturing method according to any one of (1) to (4), wherein the glass transition temperature (Tg) of the above-mentioned copolymer is 170 ° C or higher.

According to the present invention, it is possible to provide a method for producing a copolymer of a cyclic olefin copolymer having a molecular weight which is excellent in mechanical properties and which is suitable for general molding and processing, with a smaller amount of catalyst. In particular, the effect of the present invention can be further enhanced by controlling the amount of the chain transfer agent. In the present invention, since the amount of the catalyst used is small, the amount of the auxiliary catalyst can also be reduced accordingly. Therefore, it can be cheaper due to a small amount of catalysts and cocatalysts, and while maintaining the range of molecular weight, the amount of cyclic olefin copolymers per batch can be increased to save resources. In addition, since there are few catalysts and co-catalysts remaining in the obtained copolymer, it is easy to improve the transparency and mechanical properties of a molded body such as a film obtained from the copolymer.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The method for producing the copolymer of the present invention includes an α-olefin derived from at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin of C4 to C12 in the presence of a titanocene catalyst. The polymerization step in which the monomer (B) is polymerized to obtain a copolymer is that the amount of the above-mentioned copolymer obtained in the above-mentioned polymerization step is 1000 g or more per 1 g of the above titanocene catalyst, and the number of the above-mentioned copolymers The average molecular weight is 20,000 to 200,000. According to the method for producing a polymer of the present invention, even with a smaller amount of catalyst, while maintaining the range of molecular weight, more high-molecular-weight cyclic olefin copolymers can be obtained in one batch. In particular, from the viewpoint of the amount of catalyst used, and the amount and number average molecular weight of the obtained copolymer, in the production method and polymerization step of the copolymer of the present invention, together with the titanocene catalyst, It is better to carry out in the presence of a promoter and a chain transfer agent composed of aluminoxane.

[Copolymer]

The copolymer obtained by the method for producing a copolymer of the present invention includes a structural unit derived from a cyclic olefin (A) derived from norbornene and an α-olefin unit derived from an α-olefin derived from C4 to C12. The architectural unit of body (B).

The amount of the above-mentioned copolymer obtained in the polymerization step included in the above-mentioned production method is 1000 g or more, and preferably 2000 g or more, per 1 g of the titanocene catalyst used in the polymerization step.

The number average molecular weight of the copolymer of the present invention is preferably from 20,000 to 200,000, more preferably from 30,000 to 1,50,000. When the number average molecular weight is 20,000 or more, the glass transition temperature (Tg) of the obtained copolymer is unlikely to become too low. When the number average molecular weight is 200,000 or less, the viscosity of the obtained copolymer solution is unlikely to become too high. In this specification, the number average molecular weight refers to the number average molecular weight in terms of polystyrene measured by a gel permeation chromatography.

The glass transition temperature (Tg) of the copolymer of the present invention is 170 ° C or higher, preferably 200 ° C or higher, more preferably 230 ° C or higher, and particularly preferably 260 ° C or higher. If the above-mentioned glass transition temperature is above 170 ° C, the above-mentioned copolymerization is performed. Since the transparent film obtained from the composition has sufficient heat resistance, it can be suitably used, for example, as a substrate for ITO vapor deposition. In particular, if the glass transition temperature is 260 ° C or higher, the transparent film obtained from the above-mentioned copolymer has more sufficient heat resistance. Therefore, even if it is in contact with molten lead-free solder, it is unlikely to be deformed or cracked. , Melting, etc., so it can be used well for lead-free solder components. In addition, the upper limit of the glass transition temperature of the copolymer is not particularly limited, but as the glass transition temperature becomes higher, the number of structural units derived from the α-olefin in the copolymer decreases. The effect of improving the mechanical strength of copolymerization tends to decrease. The glass transition temperature is preferably 350 ° C or lower, and more preferably 330 ° C or lower. In addition, in this specification, the glass transition temperature is a value measured by a DSC method (method described in JIS K 7121) under conditions of a temperature rise rate of 20 ° C / min.

[Titanocene catalyst]

The titanocene catalyst is not particularly limited, and a known one can be used. Titanocene catalysts can be used alone or in combination of two or more.

Examples of the titanocene catalyst include those represented by the following formula (1).

R ¹ to R ³ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, hexyl, cyclopentyl, and cyclohexyl; phenyl, Aryl groups such as biphenyl, phenyl or biphenyl having the alkyl group as a substituent, naphthyl, naphthyl group having the alkyl group as a substituent, and the like.

R ⁴ and R ⁵ are each independently an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a halogen atom. Specific examples include halogens such as fluorine atom, chlorine atom, bromine atom, and iodine atom. Atoms: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, having the above halogen atom as These alkyl groups as a substituent; phenyl, biphenyl, naphthyl, these aryl groups having the above-mentioned halogen atom or alkyl group as a substituent.

R ⁶ to R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a silicon group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent. Specific examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, hexyl, heptyl, octyl, Cyclopentyl, cyclohexyl and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and the aryl group having the above-mentioned alkyl group as a substituent. Specific examples of the silyl group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and third butyl groups. Alkyl groups having 1 to 12 carbon atoms such as pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, etc., as the substituent silyl.

Specific examples of the titanocene catalyst represented by the general formula (1) include (isopropylamidoamine) dimethyl-9-fluorenylsilane dimethyl titanium, and (isobutylamidoamine) dimethyl. -9-fluorenylsilyl dimethyl titanium, (third butyl fluorenamine) dimethyl-9-fluorenyl silane dimethyl titanium, (isopropyl fluorenamine) dimethyl-9-fluorenyl silane dimethyl Titanium, (isobutylphosphonium amine) dimethyl-9- (3,6-dimethylfluorenyl) silane titanium dichloride, (third butylphosphonium amine) dimethyl-9-fluorenylsilane Titanium dichloride, (isopropylamidamine) dimethyl-9- (3,6-dimethylamidino) silane titanium dichloride, (isobutylamidamine) dimethyl-9- (3 , 6-dimethylfluorenyl) silane titanium dichloride, (third butylphosphonium amine) dimethyl-9- (3,6-dimethylfluorenyl) silane dimethyl titanium, (isopropyl Fluorenamine) dimethyl-9- (3,6-dimethylfluorenyl) silanyl titanium dichloride, (isobutylfluorenamine) dimethyl-9- (3,6-dimethylfluorenyl) Silane titanium dichloride, (third butyl fluorenamine) dimethyl-9- (3,6-dimethylfluorenyl) silane dimethyl titanium, (isopropylfluorenamine) dimethyl 9- [ 3,6-bis (third butyl) fluorenyl] silane titanium dichloride, (isobutylfluorenamine) dimethyl 9- [3,6-bis (third butyl) fluorenyl] silane dichloride Titanium (Third butylammonium amine) dimethyl 9- [3,6-bis (third butyl) fluorenyl] silyl dimethyl titanium, (isopropylamidamine) dimethyl 9- [2,7- Bis (third butyl) fluorenyl] silane titanium dichloride, (isobutyl fluorenamine) dimethyl 9- [2,7-bis (third butyl) fluorenyl] silane titanium dichloride, ( Tertiary butyl fluorenamine) dimethyl 9- [2,7-bis (third butyl) fluorenyl] silyl dimethyl titanium, (isopropyl fluorenamine) dimethyl 9- (2,3, 6,7-tetramethylfluorenyl) silyl titanium dichloride, (isobutylphosphonium amine) dimethyl 9- (2,3,6,7-tetramethylfluorenyl) silyl titanium dichloride, ( Tertiary butyl amidamine) dimethyl 9- (2,3,6,7-tetramethylamidino) silyl dimethyl titanium and the like. (Third butylammonium amine) dimethyl 9-fluorenylsilyl dimethyl titanium ((t-BuNSiMe ₂ Flu) TiMe ₂ ) is preferred. (t-BuNSiMe ₂ Flu) TiMe ₂ is a titanium complex represented by the following formula (2). For example, TiMe ₂ can be easily synthesized as described in "Macrornolecules, Vol. 31, p. 3184, 1998".

[Chemical 2]

In the formula, Me represents a methyl group, and t-Bu represents a third butyl group.

[Auxiliary catalyst composed of alkyl alumoxane]

The catalyst used in the present invention is composed of an alkylalumoxane. The above catalysts can be used alone or in combination of two or more.

The alkylaluminoxane is not particularly limited, and examples thereof include compounds represented by the following formula (3) or (4). The alkylaluminoxane represented by the following formula (3) or (4) can be obtained by reacting trialkylaluminum with water.

In the formula, R represents an alkyl group having 1 to 4 carbon atoms, n represents 0 to 40, and an integer of 2 to 30 is preferred. )

Examples of the alkylalumoxane include modified methylalumoxane in which a part of methyl groups of methylalumoxane and methylalumoxane are substituted with alkyl groups. Examples of the modified methylaluminoxane include a substituted alkyl group, and a modified methylaluminoxyl group having an alkyl group having 2 to 4 carbon atoms such as ethyl, propyl, isopropyl, butyl, and isobutyl. Alkane is preferred, and modified methylaluminoxane substituted with a part of the methyl group by isobutyl is more preferred. Specific examples of the alkylalumoxane include methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane, methylethylalumoxane, Methylbutylalumoxane, methylisobutylalumoxane and the like are preferred. Among them, methylalumoxane and methylisobutylalumoxane are preferred.

The alkylaluminoxane can be prepared by a conventional method. As the alkylaluminoxane, a commercially available product can also be used. Commercially available products of alkylalumoxane include, for example, MMAO-3A, TMAO-200 series, TMAO-340 series (all manufactured by TOSHO FINECHEM (Co., Ltd.)) or methylalumoxane solution (made by ALBEMARLE) Wait.

[Chain transfer agent]

The chain transfer agent used in the present invention is a compound having a chain transfer ability. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

The chain transfer agent is not particularly limited, and a conventional compound having a chain transfer ability can be used, and examples thereof include an aluminum alkyl. Examples of the alkyl aluminum include compounds represented by the following general formula (5).

(R ¹⁰ ) _z AlX _3-z (5)

In the formula, R ¹⁰ represents an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3.

Alkyl group having 1 to 15 carbons, for example, methyl, ethyl, n-propyl Base, isopropyl, n-butyl, isobutyl, n-octyl, and the like.

Specific examples of the aluminum alkyl include trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-secondary aluminum, and tri-n-octyl aluminum. Trialkyl aluminum; alkyl aluminum halides such as dimethyl aluminum chloride, diisobutyl aluminum chloride; alkyl aluminum hydrides such as diisobutyl aluminum hydride; dimethyl aluminum methoxy etc. Alkyl alkoxy aluminum.

As another chain transfer agent, a Chain Shuttling agent which is known as a polymerization catalyst for a metal diclocene can be used. Examples of the Chain Shuttling agent include the above-mentioned aluminum alkyl and zinc alkyl. Examples of the alkyl zinc include compounds represented by the following general formula (6).

(R ¹¹ ) _z ZnX _2-y (6)

In the formula, R ¹¹ is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8; X is a halogen atom or a hydrogen atom; and y is an integer of 0 to 2.

Examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-octyl.

Specific examples of the alkyl zinc include dimethyl zinc, diethyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-second butyl zinc aluminum, and di-n-octyl zinc Alkyl zinc, etc .; Alkyl zinc halides, such as methyl zinc chloride, isobutyl zinc chloride; Alkyl zinc hydrides, such as isobutyl zinc hydride; Alkyl alkyls, such as methyl methoxy zinc Zinc oxyhydroxide; Zinc halides such as zinc chloride.

The alkyl aluminum or alkyl zinc may be directly charged into the polymerization system, or may be charged in a state of being contained in the alkyl alumoxane. In addition, it can also be an alkylaluminum which is a raw material remaining after production when an alkylaluminoxane is produced. Alternatively, an aluminum alkyl and an alkyl zinc may be used in combination.

[Cyclic olefin monomer (A)]

The cyclic olefin monomer (A) derived from norbornene can be, for example, norbornene and substituted norbornene, preferably norbornene. The said cyclic olefin monomer (A) can be used individually by 1 type or in combination of 2 or more types.

The substituted norbornene is not particularly limited, and examples of the substituent of the substituted norbornene include a halogen atom and a monovalent or divalent hydrocarbon group. Specific examples of the substituted norbornene include those represented by the following general formula (I).

In the formula, R ¹ to R ¹² may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may also be integrated. A divalent hydrocarbon group is formed, and R ⁹ or R ¹⁰ , R ¹¹ or R ¹² may form a ring with each other.

In addition, n represents an integer of 0 or positive. When n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeated unit.

However, when n = 0, at least one of R ¹ to R ⁴ and R ⁹ to R ¹² is not a hydrogen atom.

The substituted norbornene represented by the general formula (I) will be described. R ¹ to R ¹² in the general formula (I) may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ¹ to R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having a carbon number of 1 to 20; etc., which may be different from each other, or may be partially different. It may be all the same.

Specific examples of R ⁹ to R ¹² include a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as cyclohexyl; phenyl and toluene Substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, ethylphenyl, isopropylphenyl, naphthyl, anthracenyl, etc .; benzyl, phenethyl, arylalkyl substituted with other alkyl groups, etc., which Etc. may be different from each other or partly different, and all may be the same.

Specific examples when R ⁹ and R ¹⁰ or R ¹¹ and R ^{12 are} integrated to form a divalent hydrocarbon group include, for example, ethylene, propylene, and isopropylidene groups.

When R ⁹ or R ¹⁰ , R ¹¹ or R ¹² form a ring with each other, the formed ring may be a single ring or a polycyclic ring, a bridged polycyclic ring, or a ring having a double bond. In addition, , Can also be a ring composed of a combination of these rings. These rings may have a substituent such as a methyl group.

Specific examples of the substituted norbornene represented by the general formula (I) include 5-methylbicyclo [2.2.1] hept-2-ene and 5,5-dimethylbicyclo [2.2.1] hept-2 -Ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-ethylenebicyclo [2.2.1] hept-2-ene Ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-octylbicyclo [2.2.1] hept-2-ene, 5-octadecylbicyclo [2.2.1] hept-2-ene , 5-propenylbicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, 5-propenylbicyclo [2.2.1] hept-2-ene, etc. 2-ring cyclic olefin; tricyclic [4.3.0.1 ^2,5 ] dec-3,7-diene (common name: dicyclopentadiene), tricyclic [4.3.0.1 ^2,5 ] dec-3- Ene; tricyclic [4.4.0.1 ^2,5 ] dec-3,7-diene, or tricyclic [4.4.0.1 ^2,5 ] dec-3,8-diene, or some of these hydrogen additions ( Or cyclopentadiene and cyclohexene adduct) tricyclo [4.4.0.1 ^2,5 ] dec-3-ene; 5-cyclopentyltricyclo [2.2.1] hept-2-ene, 5 -Cyclohexylbicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenylbicyclo [2.2.1] hept-2-ene, etc. cyclic olefins having 3 rings; tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene (also merely referred to as tetracyclododecene), 8 - methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 dodecene - ene, 8-methylene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-propenyl tetracyclo [4.4.0.1 ^2,5. 1 ^7,10] dodeca-3-ene, etc. the cyclic olefin ring 4; 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8 - cyclohexyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, 8-cyclohexenyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca 3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene; tetracyclo [7.4.1 ^3,6 .0 ^1,9. 0 ^2,7 ] Tetradec-4,9,11,13-tetraene (also known as 1,4-methylene-1,4,4a, 9a-tetrahydrofluorene), tetracyclic [8.4.1 ^4,7 .0 ^1,10 .0 ^3,8 ] Fifteen carbon-5,10,12,14-tetraene (also known as 1,4-methylene-1,4,4a, 5,10, 10a-hexahydroanthracene); pentacyclic [6.6.1.1 ^3,6 .0 ^2,7 .0 ^9,14 ] -4-hexadecene, pentacyclic [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] -4-pentadecene, pentacyclic [7.4.0.0 ^2,7 .1 ^3,6 .1 ^10,13 ] -4-pentadecene; heptacyclo [8.7.0.1 ^2,9 .1 ^{4 , 7} .1 ^11,17 .0 ^3,8 0 ^12,16 ] -5-eicosene, heptacyclic [8.7.0.1 ^2,9 .0 ^3,8 .1 ^7,7 .0 ^12,17 .1 ^13,16 ] -14- Eicosene; polycyclic cyclic olefins such as 4-mers of cyclopentadiene.

Among them, norbornene is substituted with alkyl (for example, bicyclo [2.2.1] hept-2-ene substituted with more than one alkyl group), and norbornene is substituted with alkylene (for example, Bicyclo [2.2.1] hept-2-ene) preferably substituted with one or more alkylene groups, and 5-ethylenebicyclo [2.2.1] hept-2-ene (common name: 5-ethylene) Ethyl-2-norbornene, or only ethylidene norbornene) is particularly preferred.

[α-olefin monomer (B)]

The α-olefin monomer (B) derived from the C4 to C12 α-olefin is, for example, a C4 to C12 α-olefin having at least one substituent such as a C4 to C12 α-olefin or a halogen atom, C4-C12 alpha-olefins are preferred, and C6-C10 alpha-olefins are more preferred.

The α-olefins of C4 to C12 are not particularly limited, such as 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl- 1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, and the like. Among them, 1-hexene, 1-octene, and 1-decene are preferred.

[Conditions of polymerization step]

The conditions of the polymerization step are not particularly limited as long as a desired copolymer can be obtained, and conventional conditions can be used, and the polymerization temperature, polymerization pressure, and polymerization time can be appropriately adjusted. Moreover, the usage-amount of each component can be illustrated as follows.

The amount of the α-olefin monomer (B) added is preferably 1 to 500 parts by mass, and more preferably 10 to 300 parts by mass for the cyclic olefin monomer (A).

The amount of the titanocene catalyst used is preferably 0.00001 to 0.1 parts by mass, and more preferably 0.0001 to 0.05 parts by mass for the cyclic olefin monomer (A).

The amount of the alkylaluminoxane used is based on 100 parts by mass of the cyclic olefin monomer (A). 0.0001 to 5 parts by mass is preferred, and 0.01 to 3 parts by mass is preferred.

The amount of the chain transfer agent to be used is preferably from 0.0001 to 10 parts by mass, and more preferably from 0.01 to 5 parts by mass for the cyclic olefin monomer (A).

[Example]

Hereinafter, examples are given to specifically explain the present invention, but the present invention should not be limited to these examples. As long as there is no special mention, the "part" indicating quantity refers to the "quality part".

[Preparation of Copolymer]

In a glass reactor which was dried and maintained under a nitrogen atmosphere, each monomer described in Table 1 and the promoter described in Table 2 were added, and after maintaining the polymerization temperature, the catalyst described in Table 2 was added. .

The catalyst and the cocatalyst were added to the reactor in a state of being dissolved in toluene, respectively. After the polymerization was continued in the reactor at the polymerization temperature and polymerization time shown in Table 3, 1 part by mass of 2-propanol was added to complete the reaction. Next, the obtained polymerization reaction solution was poured into a large amount of acidic hydrochloric acid methanol to completely precipitate the polymer. After filtering and washing, the polymer was dried under reduced pressure at 60 ° C for 1 day or more to obtain a copolymer. The mass of the obtained copolymer was measured ("yield" in Table 3). The ratio of the obtained copolymer to the amount of catalyst used ("g (copolymer) / g (catalyst)" in Table 3) was calculated.

The types of catalysts and promoters used are as follows. Here, the t-Bu system means a third butyl group, and the Flu system is a fluorenyl group.

Catalyst A: (t-BuNSiMe ₂ Flu) TiMe ₂

Catalyst A: 6.5% by mass (in terms of Al atom) of MMAO-3A toluene solution ([(CH ₃ ) _0.7 (iso-C ₄ H ₉ ) _0.3 AlO] _n methyl isobutylaluminoxane Solution, made of TOSHO FINECHEM (stock), and 6 mol% trimethylaluminum in total Al)

Catalyst B: 9.0% by mass (in terms of Al atom) TMAO-211 toluene solution (a solution of methylaluminoxane, manufactured by TOSHO FINECHEM (stock), and furthermore, it contains 26 mol% of trimethylaluminum in total Al )

Catalyst C: Triisobutyl aluminum

Catalyst D: Dimethylaniline tetrakis (pentafluorophenyl) borate

The number average molecular weight and Tg of each copolymer are shown in Table 3.

The values of "parts" in Tables 1, 2 and 3 are values for 100 parts of 2-norbornene. In addition, regarding the promoter A and the promoter B in Table 2, the value of "part" is a value of a toluene solution.

As shown in Table 3, according to the present invention, the proportion of the copolymer obtained with respect to the amount of the catalyst used is high.

Claims (5)

A method for manufacturing a copolymer, comprising: in the presence of a titanocene catalyst, at least a cyclic olefin monomer (A) derived from norbornene and an α-olefin monomer derived from a C4-C12 α-olefin (B) A polymerization step for obtaining a copolymer by polymerization, in which the amount of the copolymer obtained in the polymerization step is equal to or more than 1,000 g per 1 g of the titanocene catalyst, and the number average molecular weight of the copolymer Above 200,000 or less, the above titanocene catalyst is represented by the following formula (1),

(In formula (1), R ¹ to R ³ are independently C 1-6 alkyl or C 6 to 12 aryl, and R ⁴ and R ⁵ are independently C 1 to 12 Alkyl group, aryl group with 6 to 12 carbon atoms, or halogen atom, R ⁶ to R ¹³ are independently hydrogen atom, alkyl group with 1 to 12 carbon atoms, aryl group with 6 to 12 carbon atoms, or (Silicon group having a monovalent hydrocarbon group having 1 to 12 carbon atoms as a substituent). The manufacturing method according to item 1 of the patent application scope, wherein the polymerization step is carried out in the presence of a cocatalyst composed of an alkyl aluminoxane and a chain transfer agent together with the above titanocene catalyst. According to the manufacturing method of claim 2 of the patent application scope, wherein the above chain transfer agent is an aluminum alkyl. According to the manufacturing method of claim 3 of the patent application scope, wherein the above-mentioned alkyl aluminum series is trimethyl aluminum. The manufacturing method according to any one of items 1 to 4 of the patent application range, wherein the glass transition temperature (Tg) of the above copolymer is 170 ° C or higher.